CN114188601B - Preparation method and application of solid electrolyte - Google Patents
Preparation method and application of solid electrolyte Download PDFInfo
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- CN114188601B CN114188601B CN202111507790.9A CN202111507790A CN114188601B CN 114188601 B CN114188601 B CN 114188601B CN 202111507790 A CN202111507790 A CN 202111507790A CN 114188601 B CN114188601 B CN 114188601B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of solid electrolytes, in particular to a preparation method and application of a solid electrolyte. The invention provides a preparation method of a solid electrolytic cell, which comprises the following steps: firstly mixing sodium salt, phosphorus salt, zirconium oxide and silicon oxide, and calcining to obtain a sodium zirconium silicate phosphate precursor; and (3) after the sodium zirconium silicate phosphate precursor, the binder and the sodium metasilicate are mixed for the second time, tabletting and liquid phase sintering are sequentially carried out, so that the solid electrolyte is obtained. The solid electrolyte prepared by the preparation method has a wider electrochemical window.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a preparation method and application of a solid electrolyte.
Background
In the past decade, lithium ion batteries have been rapidly developed. However, the price increase hampers further applications of lithium ion batteries, so it is imperative to find cheaper batteries to replace lithium ion batteries. Sodium ion batteries are considered as the best energy storage means to replace lithium ion batteries due to their adequate sodium resources and low cost. Unlike organic liquid electrolytes, which are prone to leakage, flammable, and ineffective in suppressing dendrites, solid sodium electrolytes are widely used in sodium metal batteries to improve safety.
Up to now, many types of solid sodium electrolytes have been studied, such as beta-alumina type, sulfide type and sodium super-ion conductor type. The extremely high sintering temperatures (1200-1500 ℃) of the beta-alumina type and the instability of the sulfides in air limit their practical application. However, sodium super-ionic conductor type solid electrolytes such as sodium zirconium silicate phosphate may be an attractive material due to their relatively low sintering temperature, stability in air, good ionic conductivity and low thermal expansion.
The current preparation method for preparing the sodium super-ion conductor type solid electrolyte generally adopts a solid-phase sintering method, and the obtained sodium super-ion conductor type solid electrolyte has better ion conductivity but narrower electrochemical window.
Disclosure of Invention
The invention aims to provide a preparation method and application of a solid electrolyte, wherein the solid electrolyte prepared by the preparation method has a wider electrochemical window.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a solid electrolytic cell, which comprises the following steps:
firstly mixing sodium salt, phosphorus salt, zirconium oxide and silicon oxide, and calcining to obtain a sodium zirconium silicate phosphate precursor;
and (3) after the sodium zirconium silicate phosphate precursor, the binder and the sodium metasilicate are mixed for the second time, tabletting and liquid phase sintering are sequentially carried out, so that the solid electrolyte is obtained.
Preferably, the molar ratio of sodium in the sodium-containing salt, zirconium in the zirconium oxide, silicon in the silicon oxide and phosphorus in the phosphorus-containing salt is 3:2:2:1.05.
Preferably, the first mixing mode is ball milling;
the ball-milling ball material ratio is (4-6): 1, the rotating speed is 300-500 rpm, and the time is 5-12 h.
Preferably, the calcining temperature is 900-1100 ℃, the heat preservation time is 12-24 h, and the heating rate from the heating to the calcining temperature is 5-10 ℃/min.
Preferably, the mass ratio of the sodium zirconium silicate phosphate precursor to the sodium metasilicate is 100: (1-10).
Preferably, the binder is polyvinyl alcohol aqueous solution with the mass concentration of 3-5%;
the volume ratio of the total mass of the sodium zirconium silicate phosphate precursor and the sodium metasilicate to the polyvinyl alcohol aqueous solution is (500-600) mg: (50-100) mu L.
Preferably, the second mixing comprises mixing and ball milling the sodium zirconium silicate phosphate precursor and sodium metasilicate, and then mixing with a binder;
the mode of mixing ball milling is wet ball milling;
the ball milling medium of the wet ball milling is ethanol, and the ball milling ratio is (4-6): 1, the rotating speed is 300-500 rpm, and the time is 5-12 h.
Preferably, the pressure of the tabletting is 150-250 MPa, and the pressure maintaining time is 3-5 min.
Preferably, the liquid phase sintering includes a first sintering and a second sintering performed sequentially;
the temperature of the first sintering is 600-800 ℃ and the time is 2-4 h;
the temperature of the second sintering is 1000-1200 ℃ and the time is 12-24 h.
The invention also provides application of the solid electrolyte prepared by the preparation method in sodium ion batteries, wherein the solid electrolyte comprises Na 3 Zr 2 Si 2 PO 12 。
The invention provides a preparation method of a solid electrolytic cell, which comprises the following steps: firstly mixing sodium salt, phosphorus salt, zirconium oxide and silicon oxide, and calcining to obtain a sodium zirconium silicate phosphate precursor; and (3) after the sodium zirconium silicate phosphate precursor, the binder and the sodium metasilicate are mixed for the second time, tabletting and liquid phase sintering are sequentially carried out, so that the solid electrolyte is obtained. The electrolyte obtained by tabletting with the binder leaves a plurality of small holes after sintering, and the holes are filled with liquid-phase sodium metasilicate, so that the surface of the sodium zirconium silicate phosphate electrolyte has excellent positive electrode stability, and a wider electrochemical window is obtained; meanwhile, when the prepared solid electrolyte is used as the electrolyte of the sodium ion battery, the solid electrolyte can be used for enabling sodium ion transmission to be faster, so that sodium deposited on an interface to be reduced, sodium intercalation and deintercalation to be more uniform, and the possibility of sodium dendrite generation is reduced. Micro short circuit is less likely to occur in the electrolyte, and the cycle performance can be effectively improved.
Drawings
FIG. 1 is an SEM image of a solid electrolyte according to example 1;
FIG. 2 is an XRD pattern of the solid electrolyte described in example 1;
FIG. 3 is an AC impedance diagram of the solid electrolyte of example 1;
FIG. 4 is an electrochemical window diagram of the solid state electrolyte of example 1;
FIG. 5 is a polarization diagram of the solid electrolyte of example 1;
fig. 6 is an SEM image of the solid electrolyte of comparative example 1;
FIG. 7 is an XRD pattern of the solid electrolyte of comparative example 1;
FIG. 8 is an AC impedance diagram of the solid electrolyte of comparative example 1;
FIG. 9 is a graph of electrochemical window of the solid state electrolyte of comparative example 1;
FIG. 10 is a polarization graph of the solid electrolyte of comparative example 1;
fig. 11 is a graph showing the cycle performance of a symmetrical battery prepared with the solid electrolyte according to example 1;
fig. 12 is a graph showing the cycle performance of half cells prepared from the solid electrolyte of example 1;
fig. 13 is a cycle performance of a symmetrical battery prepared with the solid electrolyte of comparative example 1;
fig. 14 is a cycle performance of a half cell prepared from the solid electrolyte of comparative example 1.
Detailed Description
The invention provides a preparation method of a solid electrolytic cell, which comprises the following steps:
firstly mixing sodium salt, phosphorus salt, zirconium oxide and silicon oxide, and calcining to obtain a sodium zirconium silicate phosphate precursor;
and (3) after the sodium zirconium silicate phosphate precursor, the binder and the sodium metasilicate are mixed for the second time, tabletting and liquid phase sintering are sequentially carried out, so that the solid electrolyte is obtained.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The method comprises the steps of first mixing sodium salt, phosphorus salt, zirconium oxide and silicon oxide, and calcining to obtain a sodium zirconium silicate phosphate precursor.
In the present invention, the sodium-containing salt is preferably sodium carbonate. The phosphorus-containing salt is preferably monoammonium phosphate and/or diammonium phosphate; when the phosphorus-containing salt is two or more of the above specific choices, the proportion of the above specific substances is not particularly limited, and the above specific substances may be mixed according to any proportion. The zirconium oxide is preferably zirconium dioxide. The silicon oxide is preferably silicon dioxide.
In the present invention, the molar ratio of sodium in the sodium salt, zirconium in the zirconium oxide, silicon in the silicon oxide, and phosphorus in the phosphorus salt is preferably 3:2:2:1.05.
In the present invention, the first mixing means is preferably ball milling; the ball-milling ball material ratio is preferably (4-6): 1, more preferably (4.5 to 5.5): 1, most preferably (4.8 to 5.2): 1, a step of; the rotation speed is preferably 300 to 500rpm, more preferably 350 to 450rpm, and most preferably 380 to 420rpm; the time is preferably 5 to 12 hours, more preferably 6 to 10 hours, and most preferably 7 to 9 hours. In the invention, the ball milling is preferably wet ball milling, and the ball milling medium of the wet ball milling is preferably ethanol; the amount of ethanol used in the present invention is not particularly limited, and may be any amount known to those skilled in the art by wet ball milling.
In the present invention, the ball milling is preferably performed in a planetary ball mill.
In the invention, the ball milling conditions can ensure that the particle size of the mixed material obtained after mixing is finer, and the mixing is more uniform, thereby being beneficial to more thorough reaction of powder obtained by subsequent sintering.
After the first mixing is completed, the invention also preferably includes drying, preferably vacuum drying; the temperature of the vacuum drying is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the time is preferably 12 to 24 hours, more preferably 15 to 20 hours, most preferably 16 to 18 hours.
In the present invention, the temperature of the calcination is preferably 900 to 1100 ℃, more preferably 950 to 1050 ℃, and most preferably 980 to 1020 ℃; the heat preservation time is preferably 12-24 hours, more preferably 15-20 hours, and most preferably 16-18 hours; the heating rate to the calcination temperature is preferably 5 to 10℃per minute, more preferably 6 to 8℃per minute.
After the calcination is completed, the present invention also preferably includes cooling, and the present invention is not limited in any particular way to the cooling process, and the present invention may be cooled to room temperature by using a cooling process well known to those skilled in the art. In a specific embodiment of the invention, the cooling is preferably furnace-wise cooling.
After the cooling is completed, the invention also preferably includes grinding; the rotational speed of the grinding is not particularly limited in the present invention, and the grinding is performed by a process well known to those skilled in the art, and the grinding time is preferably 15 minutes.
In the present invention, the sodium zirconium silicate phosphate precursor includes sodium zirconium silicate phosphate and unreacted zirconium dioxide.
After obtaining a sodium zirconium silicate phosphate precursor, the invention mixes the sodium zirconium silicate phosphate precursor, a binder and sodium metasilicate for the second time, and then sequentially performs tabletting and liquid phase sintering to obtain the solid electrolyte.
In the present invention, the binder is preferably an aqueous polyvinyl alcohol solution having a mass concentration of 3 to 5%, more preferably a mass concentration of 5%; the polyvinyl alcohol aqueous solution is preferably prepared by mixing polyvinyl alcohol and water to obtain the polyvinyl alcohol aqueous solution. In the present invention, the mixing is preferably performed under the conditions of an oil bath and stirring; the temperature of the oil bath is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the time is preferably 0.5 to 1.5 hours, more preferably 0.8 to 1.2 hours. The stirring rate of the present invention is not particularly limited, and may be carried out at a rate well known to those skilled in the art.
In the invention, the addition of the binder can enable the electrolyte sheet to become more compact under the same pressure, thereby reducing the sintering temperature; the addition of the binder can lead the surface of the electrolyte to have excellent positive electrode stability, thereby obtaining a wider electrochemical window; meanwhile, the adhesive can also effectively improve the strength of the unsintered electrolyte sheet, so that the unsintered electrolyte sheet can be formed into a compact electrolyte sheet only by lower pressure, and the adhesive is beneficial to industrial production.
In the invention, the volume ratio of the total mass of the sodium zirconium silicate phosphate precursor and the sodium metasilicate to the polyvinyl alcohol aqueous solution is preferably (500-600) mg: (50 to 100) mu L, more preferably (510 to 560) mg: (60-90) mu L, most preferably (520-540) mg: (70-80) mu L.
In the invention, the mass ratio of the sodium zirconium silicate phosphate precursor to the sodium metasilicate is preferably 100: (1 to 10), more preferably 100: (2-8), most preferably 100: (5).
In the invention, in the sintering process, besides the sodium metasilicate is melted into a liquid phase at high temperature, the crystal grains of the sodium zirconium silicate phosphate can be more compact, and the density of the electrolyte is improved; simultaneously adding the sodium metasilicate can enable the sodium metasilicate to be melted at the grain boundary of the sodium zirconium silicate phosphate in the subsequent sintering process, and diffuse sodium and silicon elements to the crystal grains of the sodium zirconium silicate phosphate; meanwhile, the sodium ion transmission channel is adjusted by further adjusting the proportion of the sodium zirconium silicate phosphate, the activation energy is reduced, and the ion conductivity of the electrolyte is greatly improved.
In the present invention, the second mixing preferably includes mixing the sodium zirconium silicate phosphate precursor and sodium metasilicate, ball milling, and then mixing with a binder.
The invention also preferably comprises grinding, wherein the grinding time is preferably 5-15 min, more preferably 8-12 min, before the mixed ball milling is carried out; the rotational speed of the grinding is not particularly limited, and may be carried out at a rotational speed well known to those skilled in the art.
In the invention, the mode of mixing ball milling is wet ball milling; the ball milling medium of the wet ball milling is ethanol, and the ball milling ratio is (4-6): 1, more preferably (4.5 to 5.5): 1, most preferably (4.8 to 5.2): 1, a step of; the rotation speed is preferably 300 to 500rpm, more preferably 350 to 450rpm, and most preferably 380 to 420rpm; the time is preferably 5 to 12 hours, more preferably 6 to 10 hours, and most preferably 7 to 9 hours. The amount of ethanol used in the present invention is not particularly limited, and may be any amount known to those skilled in the art by wet ball milling.
After the completion of the mixing ball milling, the present invention also preferably includes drying. In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the time is preferably 12 to 24 hours, more preferably 15 to 20 hours.
In the present invention, the mixing with the binder is preferably performed by grinding; the grinding process is not particularly limited in the present invention, and the process known to those skilled in the art may be adopted to completely coat the binder on the surface of the particles (a mixture of the sodium zirconium silicate phosphate precursor and sodium metasilicate).
In the present invention, the pressure of the tablet is preferably 150 to 250MPa, more preferably 180 to 220MPa, and most preferably 200MPa; the dwell time is preferably 3 to 5 minutes, more preferably 3.5 to 4.5 minutes, most preferably 4 minutes.
In the present invention, the liquid phase sintering is preferably performed in an air atmosphere or an oxygen atmosphere; the liquid phase sintering preferably includes a first sintering and a second sintering which are sequentially performed; the temperature of the first sintering is preferably 600-800 ℃, more preferably 650-750 ℃, and most preferably 680-720 ℃; the time is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, most preferably 3 hours; the temperature of the second sintering is preferably 1000-1200 ℃, more preferably 1050-1150 ℃; the time is preferably 12 to 24 hours, more preferably 15 to 18 hours.
After the completion of the liquid phase sintering, the present invention also preferably includes cooling. The cooling mode is not particularly limited in the present invention, and may be performed in a manner well known to those skilled in the art. In a specific embodiment of the invention, the cooling is specifically furnace-following cooling.
The invention also provides application of the solid electrolyte prepared by the preparation method in sodium ion batteries, wherein the solid electrolyte comprises Na 3 Zr 2 Si 2 PO 12 . The invention has no special method for the applicationThe application is limited by methods well known to those skilled in the art.
The following describes the preparation method and application of the solid electrolyte provided in the present invention in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
0.9937g of sodium carbonate, 1.5403g of zirconium dioxide, 0.7511g of silicon dioxide and 0.7548g of ammonium dihydrogen phosphate are placed in a planetary ball mill, 24g of zirconium oxide balls and 4mL of ethanol are added for mixed ball milling, and the rotation speed of the mixed ball milling is 400rpm, and the time is 12 hours; vacuum drying at 80 ℃ for 12 hours, calcining at 1000 ℃ for 12 hours in air atmosphere, cooling to room temperature, and grinding for 15 minutes to obtain a sodium zirconium silicate phosphate precursor;
mixing 1.025g of polyvinyl alcohol and 23.75g of deionized water, and carrying out oil bath at 80 ℃ for 1h under stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
3.2g of the sodium zirconium silicate phosphate precursor and 0.16g of sodium metasilicate (5% of the sodium zirconium silicate phosphate precursor) are placed in a planetary ball mill, 24g of zirconia and 4mL of ethanol are added for ball milling, and the ball milling speed is 400rpm and the time is 12h; vacuum drying at 80 ℃ for 12 hours to obtain a mixed material;
530mg of the mixed material and 50 mu L of polyvinyl alcohol aqueous solution are ground until the polyvinyl alcohol aqueous solution is completely coated on the surfaces of the particles, poured into a die with the diameter of 16mm, and pressed for 4min under 150MPa to obtain an electrolyte sheet with the thickness of 1.2 mm;
sequentially performing first sintering and second sintering on the electrolyte sheet; the temperature of the first sintering is 800 ℃ and the time is 4 hours; the second sintering temperature was 1100 ℃ for 12 hours, and cooling was performed to obtain a solid electrolyte (ion conductivity of 1.80×10 -4 S·cm -1 The electrochemical window was 4.83V and the electron conductivity was 6.24x10 –7 S·cm –1 Sodium ion migration number of 0.9965);
SEM test and XRD test are carried out on the solid electrolyte, and the test results are shown in figures 1-2, wherein figure 1 is an SEM diagram of the solid electrolyte, and figure 2 is an XRD diagram of the solid electrolyte; as can be seen from fig. 1 to 2, the solid electrolyte sheet has a compact structure and no impurity phase generation;
fig. 3 is an ac impedance diagram of the solid electrolyte, and it can be seen from fig. 3 that the semicircle part is a high frequency region, the slant line part is a low frequency region, and the impedance of the electrolyte is 331 Ω from the junction between the high frequency and the low frequency in the diagram;
FIG. 4 is a graph showing electrochemical windows of the solid electrolyte, and it can be seen from FIG. 4 that the electrochemical stability window is 4.83V from the abscissa of the intersection of the horizontal line and the oblique line;
fig. 5 is a polarization diagram of the solid electrolyte, and as can be seen from fig. 5, the current at the steady state is 0.104 μa.
Comparative example 1
0.9937g of sodium carbonate, 1.5403g of zirconium dioxide, 0.7511g of silicon dioxide and 0.7548g of ammonium dihydrogen phosphate are placed in a planetary ball mill, 24g of zirconium oxide balls and 4mL of ethanol are added for mixed ball milling, and the rotation speed of the mixed ball milling is 400rpm, and the time is 12 hours; vacuum drying at 80 ℃ for 12 hours, calcining at 1000 ℃ for 12 hours in air atmosphere, cooling to room temperature, and grinding for 15 minutes to obtain a sodium zirconium silicate phosphate precursor;
mixing 1.25g of polyvinyl alcohol and 23.75g of deionized water, and carrying out oil bath at 80 ℃ for 1h under the condition of stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
placing 3.2g of the sodium zirconium silicate phosphate precursor into a planetary ball mill, adding 24g of zirconia and 4mL of ethanol, and performing ball milling at 400rpm for 12 hours; vacuum drying at 80 ℃ for 12 hours to obtain a ball abrasive;
530mg of the ball grinding material and 50 mu L of the polyvinyl alcohol aqueous solution are ground until the polyvinyl alcohol aqueous solution is completely coated on the surfaces of the particles, poured into a die with the diameter of 16mm, and pressed for 4min under 150MPa to obtain an electrolyte sheet with the thickness of 1.2 mm;
sequentially performing first sintering and second sintering on the electrolyte sheet; the temperature of the first sintering is 800 ℃ and the time is 4 hours; the temperature of the second sintering is 1100 ℃ and the time is 12 hours, and the solid state electrolysis is obtained after coolingMass (ion conductivity 5.12X10) -5 S·cm -1 The electrochemical window was 4.50V and the electron conductivity was 7.41×10 -7 S·cm –1 Sodium ion migration number 0.9855);
SEM test and XRD test are carried out on the solid electrolyte, and the test results are shown in figures 6-7, wherein figure 6 is an SEM diagram of the solid electrolyte, and figure 7 is an XRD diagram of the solid electrolyte; as can be seen from fig. 6 to 7, the crystal grains in the solid electrolyte sheet are small and the impurity phase zirconium dioxide is present;
fig. 8 is an ac impedance diagram of the solid electrolyte, and as can be seen from fig. 3, the semicircle part is a high frequency region, the oblique line part is a low frequency region, and the impedance of the electrolyte is 1166Ω from the junction between the high frequency and the low frequency in the diagram;
FIG. 9 is a diagram of electrochemical window of the solid electrolyte, and as can be seen from FIG. 4, the electrochemical stability window is 4.50V, which is obtained by making tangential lines of horizontal line and oblique line respectively, and from the abscissa of their intersection point;
fig. 10 is a polarization graph of the solid electrolyte, and as can be seen from fig. 5, the current at steady state is 0.124 μa.
In conclusion, the preparation method can remarkably improve the ion conductivity, the electrochemical window and the sodium ion migration number of the solid electrolyte.
Test example 1
The solid electrolyte described in example 1 was placed with two sodium sheets of 14mm diameter and 0.7mm thickness in a CR2032 battery case, in the order sodium sheet-electrolyte-sodium sheet. The cells were then tested at 0.1mA cm by pressing them into symmetrical cells under a pressure of 12.5MPa -2 0.1mAh cm -2 Is a cyclic performance of (c). The test results are shown in fig. 11. The symmetrical cell remained stable after 400h cycle, showing stable intercalation and deintercalation of sodium.
Mixing and grinding sodium vanadium phosphate, carbon black and polyvinylidene fluoride according to the proportion of 160mg to 20mg, adding 980mg of N-methylpyrrolidone, stirring for 5h, and pouring the slurry on an aluminum foil. After drying, the mixture was cut into 14mm round positive plates, each having an active material loading of 1.84mg. Electrolytic sintering of positive plate and liquid phaseSodium sheets with a mass and diameter of 14mm and a thickness of 0.7mm were placed in a CR2025 battery case, in order of positive electrode sheet-electrolyte-sodium sheet. A pressure of 12.5MPa was applied to press half cells, and then the cells were tested for cycle performance at a current density of 0.1C and a voltage range of 2.0 to 4.0V. The test results are shown in fig. 12: the half cell had a capacity of 92.4 mAh.g after 100 cycles at 0.1C -1 The capacity retention rate is as high as 96.6%.
Test example 2
The electrolyte obtained by solid phase sintering and two sodium sheets with the diameter of 14mm and the thickness of 0.7mm are placed in a CR2032 battery shell, and the sequence is sodium sheet-electrolyte-sodium sheet. The cells were then tested at 0.1mA cm by pressing them into symmetrical cells under a pressure of 12.5MPa -2 0.1mAh cm -2 Is a cyclic performance of (c). The test results are shown in fig. 13. The symmetrical cell exhibited an unstable polarization at only 35h, at which the polarization voltage was as high as 0.735V, indicating that sodium intercalation and deintercalation was unstable in the symmetrical cell.
Mixing and grinding sodium vanadium phosphate, carbon black and polyvinylidene fluoride according to the proportion of 160mg to 20mg, adding 980mg of N-methylpyrrolidone, stirring for 5h, and pouring the slurry on an aluminum foil. After drying, the mixture was cut into 14mm round positive plates, each having an active material loading of 1.84mg. The positive electrode sheet, the solid phase sintered electrolyte and a sodium sheet with a diameter of 14mm and a thickness of 0.7mm were placed in a CR2025 battery case, in that order. A pressure of 12.5MPa was applied to press half cells, and then the cells were tested for cycle performance at a current density of 0.1C and a voltage range of 2.0-4.0V. The test results are shown in fig. 12: the half cell had a capacity of 86.9 mAh.g after 100 cycles at 0.1C -1 The capacity retention rate was 95.9%, which is lower than that of the half cell assembled with the liquid phase sintered electrolyte.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A method of preparing a solid electrolyte comprising the steps of:
firstly mixing sodium salt, phosphorus salt, zirconium oxide and silicon oxide, and calcining to obtain a sodium zirconium silicate phosphate precursor;
after the sodium zirconium silicate precursor, the binder and the sodium metasilicate are mixed for the second time, tabletting and liquid phase sintering are sequentially carried out, so that the solid electrolyte is obtained; the binder is polyvinyl alcohol aqueous solution with the mass concentration of 3-5%;
the liquid phase sintering comprises a first sintering and a second sintering which are sequentially carried out;
the temperature of the first sintering is 600-800 ℃ and the time is 2-4 h;
the temperature of the second sintering is 1000-1200 ℃ and the time is 12-24 h.
2. The method of claim 1, wherein the molar ratio of sodium in the sodium-containing salt, zirconium in the zirconium oxide, silicon in the silicon oxide, and phosphorus in the phosphorus-containing salt is 3:2:2:1.05.
3. The method of claim 1, wherein the first mixing is by ball milling;
the ball-milling ball material ratio is (4-6): 1, the rotating speed is 300-500 rpm, and the time is 5-12 h.
4. The method according to claim 1, wherein the calcination temperature is 900 to 1100 ℃, the holding time is 12 to 24 hours, and the heating rate to the calcination temperature is 5 to 10 ℃/min.
5. The method of claim 1, wherein the mass ratio of the sodium zirconium silicate phosphate precursor to sodium metasilicate is 100: (1-10).
6. The method of claim 1, wherein the volume ratio of the total mass of the sodium zirconium silicate phosphate precursor and sodium metasilicate to the aqueous solution of polyvinyl alcohol is (500-600) mg: (50-100) mu L.
7. The method of making according to claim 1, 5 or 6, wherein the second mixing comprises mixing the sodium zirconium silicate phosphate precursor and sodium metasilicate, ball milling, and then mixing with a binder;
the mode of mixing ball milling is wet ball milling;
the ball milling medium of the wet ball milling is ethanol, and the ball milling ratio is (4-6): 1, the rotating speed is 300-500 rpm, and the time is 5-12 h.
8. The process according to claim 1, wherein the tabletting is carried out at a pressure of 150 to 250MPa and a dwell time of 3 to 5min.
9. Use of the solid electrolyte prepared by the preparation method according to any one of claims 1 to 8 in sodium ion batteries, wherein the solid electrolyte comprises Na 3 Zr 2 Si 2 PO 12 。
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